JP4316364B2 - Curing method for hardened cement and method for reducing drying shrinkage of hardened cement - Google Patents
Curing method for hardened cement and method for reducing drying shrinkage of hardened cement Download PDFInfo
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Description
主に土木、建築分野において使用されるセメント硬化体の養生方法およびセメント硬化体の乾燥収縮低減方法に関する。 The present invention relates to a curing method for a hardened cement body and a method for reducing drying shrinkage of the hardened cement body, which are mainly used in the fields of civil engineering and construction.
養生とは、セメントコンクリートの硬化作用を充分に発揮させるため、適当な温度と湿度とを確保し、外力が加わらないように保護しておくことである。
そして、養生によって、セメントコンクリートの水和反応が促進し、強度発現性が、また、膨張性能が向上し、乾燥収縮低減効果を発揮するものである。
Curing is to secure an appropriate temperature and humidity and to prevent external force from being applied in order to sufficiently exert the hardening action of cement concrete.
The curing promotes the hydration reaction of cement concrete, improves the strength development, improves the expansion performance, and exhibits a drying shrinkage reducing effect.
コンクリート建築・構造物において、通常行なわれている養生方法としては、シートで覆ったり、撒水したり、養生剤を撒布したりすることが挙げられ、表面のコンクリートを湿潤に保ち型枠の設置期間の調整が行なわれている(非特許文献1参照)。
しかしながら、床等、打設面の表面積が大きい場合、養生を行うことは大変な労力や費用を要するなどの課題があり、養生剤を撒布した場合も、撒布効果が得られなかったり、変色等を生じる場合があるなどの課題があった。
In concrete buildings and structures, the usual curing methods include covering with sheets, flooding, and spreading curing agents. (See Non-Patent Document 1).
However, when the surface area of the placement surface such as floor is large, there is a problem that it takes a lot of labor and expense to perform the curing, and even if the curing agent is distributed, the distribution effect cannot be obtained, discoloration, etc. There was a problem such as that may occur.
また、コンクリート二次製品においては、常温養生、蒸気養生、及びオートクレーブ養生が行われ、蒸気養生やオートクレーブ養生では、早い時期に脱型が行なわれている。
特に、膨張材を含有したセメント硬化体の二次製品においては、脱型後に、水中養生、撒水養生が望ましい。
Moreover, in concrete secondary products, normal temperature curing, steam curing, and autoclave curing are performed, and demolding is performed at an early stage in steam curing and autoclave curing.
In particular, in a secondary product of a hardened cement body containing an expanding material, underwater curing and submerged curing are desirable after demolding.
しかしながら、大きな部材や大量の部材を水中養生する場合、設備が大型となったり、その維持管理に多大な労力と費用を要するという課題があった。
また、撒水養生は、部材の内外に均一に撒水することが難しく、大量の水を消費し、冬季には水が凍結する場合が生じるという課題があった。
さらに、蒸気養生を行った場合にも、脱型時にはコンクリート温度が屋内の温度より高い場合が多く、コンクリート中の水分の飛散による膨張量の減少を生じるという課題があった。
However, when a large member or a large number of members are cured underwater, there is a problem that the equipment becomes large or requires a lot of labor and cost for its maintenance.
In addition, it is difficult for water curing to be uniformly watered in and out of the member, and a large amount of water is consumed, and there is a problem that water may freeze in winter.
Furthermore, even when steam curing is performed, the concrete temperature is often higher than the indoor temperature during demolding, and there is a problem in that the amount of expansion is reduced due to the scattering of moisture in the concrete.
一方、セメント硬化体の乾燥収縮低減方法としては、従来から、セメント混和材として収縮低減剤が使用されている。 On the other hand, as a method for reducing dry shrinkage of a hardened cement, a shrinkage reducing agent has been conventionally used as a cement admixture.
収縮低減剤は、セメント硬化体中の乾燥収縮を減らす材料として、壁や床スラブなどの一般建築物や、道路の拡幅に伴う一般構造物や、さらには、セメント製品にも使用され、乾燥収縮防止や硬化収縮の補償等をする用途に使用されている。 Shrinkage reducing agents are used as materials for reducing drying shrinkage in hardened cementitious materials, and are also used in general buildings such as walls and floor slabs, general structures accompanying road widening, and cement products. It is used for applications such as prevention and compensation for cure shrinkage.
特に、収縮低減剤として、膨張材は、通常使用され、その使用量を、コンクリート1m3当たり、20〜30kg程度と少なくして、壁、屋根スラブ、及び床材等の一般建築物や、水槽やプールなどの水理構造物、舗装、床版、並びに、ボックスカルバートなどの一般構造物や二次製品に使用され、乾燥収縮防止や硬化収縮の補償等をすることが知られている(非特許文献2参照)。 In particular, expansion materials are usually used as shrinkage reducing agents, and the amount of use is reduced to about 20 to 30 kg per 1 m 3 of concrete, and general buildings such as walls, roof slabs, and floor materials, and water tanks. It is used for hydraulic structures such as water and pools, pavements, floor slabs, and general structures and secondary products such as box culverts, and is known to prevent drying shrinkage and compensate for shrinkage due to curing (non- (See Patent Document 2).
しかしながら、現場における膨張材等の収縮低減剤を含有したセメント硬化体の、養生後の強度は、所定の設計強度までは達しておらず、水分の飛散によるセメントの水和の阻害や乾燥収縮を大きく生じる場合があり、その結果、所定のひび割れに対する抵抗性が低下する場合があった。 However, the strength after curing of the hardened cement containing shrinkage reducing agents such as expansion materials in the field does not reach the specified design strength, which inhibits the hydration of the cement due to moisture scattering and the drying shrinkage. In some cases, the resistance to a predetermined crack may be lowered.
本発明は、前記課題を解消すべく種々検討した結果なされたもので、特定の養生被覆剤を被覆することにより、乾燥収縮量が小さくなるとともに、高いひび割れ抵抗性が得られる養生方法とすることや乾燥収縮低減方法とすることを目的とする。 The present invention has been made as a result of various studies to solve the above-mentioned problems. By coating with a specific curing coating, the drying shrinkage amount can be reduced, and a curing method can be obtained which can obtain high crack resistance. And a method for reducing drying shrinkage.
即ち、本発明は、セメント硬化体に、合成樹脂水性分散体、水溶性樹脂、膨潤力が20ml/2g以上の高膨潤性粘土鉱物、及び架橋剤を主成分とする養生被覆剤を被覆するセメント硬化体の養生方法であり、前記養生被覆剤が、水溶性樹脂と膨潤力が20ml/2g以上の高膨潤性粘土鉱物とをあらかじめ水中で混合した後に、合成樹脂水性分散体と架橋剤を混合して合成されたものである前記養生方法であり、前記養生被覆剤の被覆量が固形分換算で4〜160g/m2である前記養生方法であり、前記セメント硬化体が、セメントと膨張材とを含有してなる、又は、セメントと乾燥収縮低減剤とを含有してなるセメントコンクリートからなる前記養生方法である。
さらに、本発明は、セメント硬化体に、合成樹脂水性分散体、水溶性樹脂、膨潤力が20ml/2g以上の高膨潤性粘土鉱物、及び架橋剤を主成分とする養生被覆剤を被覆するセメント硬化体の乾燥収縮低減方法であり、前記養生被覆剤が、水溶性樹脂と膨潤力が20ml/2g以上の高膨潤性粘土鉱物とをあらかじめ水中で混合した後に、合成樹脂水性分散体と架橋剤を混合して合成されたものである前記乾燥収縮低減方法であり、前記養生被覆剤の被覆量が固形分換算で4〜160g/m2である前記乾燥収縮低減方法であり、前記セメント硬化体が、セメントと膨張材とを含有してなる、又は、セメントと乾燥収縮低減剤とを含有してなるセメントコンクリートからなる前記乾燥収縮低減方法である。
That is, the present invention is coated on the hardened cement, synthetic resin aqueous dispersion, a water-soluble resins, highly swellable clay mineral Rise Junryoku is more than 20 ml / 2 g, and a curing coating consisting mainly of cross-linking agent a curing method of the cured cement to the curing coating agent is, after the water-soluble resin and the swelling force is premixed in water and 20 ml / 2 g or more highly swellable clay mineral, and synthetic resin aqueous dispersion a mixed crosslinking agent is synthesized the curing process, the coating amount of the curing coating is the regimen is 4~160g / m 2 in terms of solid content, the hardened cement paste is, In the curing method , the cement is made of cement concrete containing an expansion material or cement and a drying shrinkage reducing agent .
Furthermore, the present invention is coated on the hardened cement, synthetic resin aqueous dispersion, a water-soluble resins, highly swellable clay mineral Rise Junryoku is more than 20 ml / 2 g, and a curing coating consisting mainly of cross-linking agent to a drying shrinkage-reducing method of hardened cement paste, the curing coating agent is, after the water-soluble resin and the swelling force is premixed in water and highly swellable clay mineral described above 20 ml / 2 g, synthetic resin aqueous dispersion a mixed body with a crosslinking agent is synthesized the shrinkage reducing method, the coating amount of the curing coating is the drying shrinkage-reducing method is 4~160g / m 2 in terms of solid content, In the drying shrinkage reducing method , the hardened cement body includes cement and an expansion material, or is made of cement concrete including a cement and a drying shrinkage reducing agent.
本発明の方法で養生した膨張材使用のセメント硬化体は、膨張量が得られ、乾燥収縮が小さくなるとともに、高いひび割れ抵抗性が得られる効果を有する。 The cement-cured body using the expansion material cured by the method of the present invention has an effect that an expansion amount is obtained, drying shrinkage is reduced, and high crack resistance is obtained.
以下、本発明を詳細に説明する。
本発明でいうセメントコンクリートとは、セメントペースト、モルタル、及びコンクリートを総称するものである。
また、セメント硬化体とは、セメントペースト、モルタル、コンクリートなどの硬化体を総称するものである。
なお、本発明における部や%は特に規定しない限り質量基準で示す。
Hereinafter, the present invention will be described in detail.
The cement concrete referred to in the present invention is a general term for cement paste, mortar, and concrete.
The hardened cement body is a general term for hardened bodies such as cement paste, mortar, and concrete.
In the present invention, “parts” and “%” are based on mass unless otherwise specified.
本発明は、セメント硬化体に、養生被覆剤を被覆するセメント硬化体の養生方法、又は乾燥収縮低減方法に関するものである。
本発明のセメント硬化体は、セメントと収縮低減剤を含有するセメントコンクリートからなるものが好ましい。
The present invention relates to a curing method for a cured cement or a method for reducing drying shrinkage, in which a cured cement is coated with a curing coating agent.
The cement hardened body of the present invention is preferably made of cement concrete containing cement and a shrinkage reducing agent.
ここで、セメントとしては、普通、早強、超早強、低熱、及び中庸熱のポルトランドセメントや、これらポルトランドセメントに、高炉スラグ、フライアッシュ、又はシリカを混合した各種混合セメント、並びに、エコセメント、白色セメント、及び超速硬セメント、シリカフューム、フライアッシュ、及びけい酸白土等のポゾラン反応を有するものや高炉スラグ微粉末等を混和したポルトランドセメント、並びに、石灰石微粉末等を混合したフィラーセメントなどが挙げられる。 Here, normal, early strong, super early strong, low heat, and moderately hot Portland cements, various mixed cements in which blast furnace slag, fly ash, or silica is mixed with these Portland cements, and eco cements are used. , White cement, super fast cement, silica fume, fly ash, and those with pozzolanic reaction such as silicate clay, Portland cement mixed with blast furnace slag fine powder, filler cement mixed with limestone fine powder, etc. Can be mentioned.
また、収縮低減剤は、セメント硬化体の乾燥収縮を減らす材料として使用され、具体的には、無機系収縮低減剤や、有機系収縮低減剤があり、無機系収縮低減剤としては、石膏、膨張材、及び炭酸カルシウムなどが、また、有機系収縮低減剤としては、乾燥収縮低減剤等が使用されている。
収縮低減剤は、壁や床スラブなどの一般建築物や、道路の拡幅に伴う一般構造物や、さらには、セメント製品にも使用され、乾燥収縮防止や硬化収縮の補償等をする用途に使用されている。
本発明では、収縮低減剤として、膨張材や乾燥収縮低減剤を使用することが、ひび割れの面から好ましい。
In addition, the shrinkage reducing agent is used as a material for reducing the drying shrinkage of the hardened cement, and specifically includes an inorganic shrinkage reducing agent and an organic shrinkage reducing agent. As the inorganic shrinkage reducing agent, gypsum, Intumescent materials, calcium carbonate, and the like, and dry shrinkage reducing agents and the like are used as organic shrinkage reducing agents.
Shrinkage reducing agents are also used in general buildings such as walls and floor slabs, general structures accompanying road widening, and cement products, and are used for applications such as drying shrinkage prevention and hardening shrinkage compensation. Has been.
In the present invention, it is preferable from the viewpoint of cracking that an expansion material or a drying shrinkage reducing agent is used as the shrinkage reducing agent.
膨張材としては特に限定されるものではないが、CaO-Al2O3-Fe2O3系化合物のカルシウムアルミノフェライト系膨張材や、CaO-Al2O3-SO3系化合物のカルシウムサルフォアルミネート系膨張材が挙げられる。
膨張材の粒度は特に限定されるものではないが、通常、ブレーン比表面積(以下、ブレーン値という)で1,500〜4,500cm2/gが好ましい。1,500cm2/g未満では未反応物が長期間残存し、耐久性を低下させる場合があり、4,500cm2/gを超えると水和反応が早く、所定の膨張性能が得られない場合がある。
膨張材の使用量は、セメント100部に対して、5〜18部が好ましい。5部未満では充分な乾燥収縮防止効果が得られない場合があり、18部を超えると膨張量が大きすぎて強度低下する場合がある。
The expansion material is not particularly limited, but a CaO—Al 2 O 3 —Fe 2 O 3 compound calcium aluminoferrite expansion material or a CaO—Al 2 O 3 —SO 3 compound calcium sulfone is used. An aluminate expansion material is mentioned.
The particle size of the expansion material is not particularly limited, but it is usually preferably 1,500 to 4,500 cm 2 / g in terms of specific surface area of brain (hereinafter referred to as “brain value”). If it is less than 1,500 cm 2 / g, unreacted substances may remain for a long period of time, and the durability may be lowered. If it exceeds 4,500 cm 2 / g, the hydration reaction is fast and the prescribed expansion performance may not be obtained. .
The amount of the expansion material used is preferably 5 to 18 parts with respect to 100 parts of cement. If it is less than 5 parts, a sufficient drying shrinkage preventing effect may not be obtained, and if it exceeds 18 parts, the expansion may be too large and the strength may be reduced.
乾燥収縮低減剤は、ノニオン系界面活性剤の一種であって、通常、純分99%以上の液体や粉体で、セメント硬化体中の細孔にある水に溶解して、蒸発するときの水の表面張力を低下させるものである。
乾燥収縮低減剤の基本構造は、ポリオキシアルキレン重合物を有し、末端に低級アルコール、フェノール、及びアミノ結合物を付加したものである。
具体的には、ポリプロピレングリコール、エチレンオキシドメタノール付加物エチレンオキシド・プロピレンオキシドブロック重合物、エチレンオキシド・プロピレンオキシドランダム重合物、グリコールのシクロアルキル基付加物、グリコールの両端にメチル基を付加した付加物、グリコールのフェニル基付加物、グリコールにメチルフェニル基を付加したブロック重合物、グリコールの両端にエチレンオキサイドメタノールを付加した付加物、及びグリコールにジメチルアミンを付加した付加物等が使用可能である。
乾燥収縮低減剤は、セメントに混和することも可能であるが、セメント硬化体に被覆して浸透させることも可能である。
セメントに混和する場合の乾燥収縮低減剤の使用量は、セメント100部に対して、1〜6部が好ましく、2〜4部がより好ましい。1部未満では所定の乾燥収縮低減効果を得ることが難しい場合があり、6部を超えると強度発現が遅れたり、乾燥収縮低減効果が頭打ちになりコストパフォーマンスが悪くなる場合がある。
乾燥収縮低減剤のセメント硬化体に被覆する使用量は、セメント硬化体50〜400g/m2が好ましく、100〜300g/m2がより好ましい。50g/m2未満では所定の乾燥収縮低減効果を得ることが難しい場合があり、400g/m2を超えると乾燥収縮低減効果が頭打ちになり作業時間がかかりコストパフォーマンスが悪くなる場合がある。
本発明における被覆の順序は、乾燥収縮低減剤をセメント硬化体に被覆し、その後に、養生被覆剤を被覆することが好ましい。
Drying shrinkage reducing agent is a kind of nonionic surfactant, which is usually a liquid or powder with a pure content of 99% or more, dissolved in water in the pores of hardened cement and evaporated. It reduces the surface tension of water.
The basic structure of the drying shrinkage reducing agent has a polyoxyalkylene polymer, and a lower alcohol, phenol, and amino bond are added to the terminal.
Specifically, polypropylene glycol, ethylene oxide methanol adduct ethylene oxide / propylene oxide block polymer, ethylene oxide / propylene oxide random polymer, glycol cycloalkyl group adduct, glycol adducts with methyl groups added to both ends of glycol, glycol A phenyl group adduct, a block polymer obtained by adding a methylphenyl group to glycol, an adduct obtained by adding ethylene oxide methanol to both ends of glycol, an adduct obtained by adding dimethylamine to glycol, or the like can be used.
The drying shrinkage reducing agent can be mixed with the cement, but can also be coated and penetrated into the hardened cement body.
The amount of the drying shrinkage reducing agent used in the cement is preferably 1 to 6 parts, more preferably 2 to 4 parts, with respect to 100 parts of cement. If it is less than 1 part, it may be difficult to obtain a predetermined drying shrinkage reduction effect, and if it exceeds 6 parts, strength development may be delayed, or the drying shrinkage reduction effect may reach its peak, resulting in poor cost performance.
The amount of coating to the hardened cement drying shrinkage-reducing agent is preferably hardened cement paste 50~400g / m 2, 100~300g / m 2 is more preferable. If it is less than 50 g / m 2 , it may be difficult to obtain a predetermined drying shrinkage reduction effect, and if it exceeds 400 g / m 2 , the drying shrinkage reduction effect will reach its peak, and it may take time to work and cost performance may deteriorate.
The order of coating in the present invention is preferably that the dry shrinkage reducing agent is coated on the hardened cement body, and thereafter the curing coating agent is coated.
本発明で使用する骨材としては、通常のモルタルやコンクリートに使用できるものであれば特に限定されるものではなく、川砂、陸砂、砕砂、及び海砂等の細骨材や、川砂利、砕石、及び人工軽量骨材等の粗骨材が挙げられる。 The aggregate used in the present invention is not particularly limited as long as it can be used for ordinary mortar and concrete, and fine aggregates such as river sand, land sand, crushed sand, and sea sand, river gravel, Examples include coarse aggregates such as crushed stones and artificial lightweight aggregates.
本発明では、さらに、減水剤を使用することが可能である。
減水剤は、コンクリートの流動性を改善したり、単位水量を低減させるために使用するもので、高耐久性、高強度発現性、及び高流動性のコンクリートを得ることが可能となるものである。JIS A 6204に、コンクリート用化学混和剤として1982年に制定されている。
In the present invention, it is further possible to use a water reducing agent.
The water reducing agent is used to improve the fluidity of concrete or reduce the unit water volume, and it is possible to obtain a concrete having high durability, high strength, and high fluidity. . Established in 1982 as a chemical admixture for concrete in JIS A 6204.
減水剤としては、AE減水剤、高性能減水剤、及び高性能AE減水剤等が使用可能である。具体的には、AE減水剤としては、リグニンスルホン酸化合物、変性リグニンスルホン酸化合物、ポリオール、及びオキシカルボン酸化合物等が挙げられ、高性能減水剤としては、ナフタレンスルホン酸塩のホルマリン縮合物やメラミンスルホン酸のホルマリン縮合物等が挙げられ、高性能AE減水剤としは、ポリスチレンスルホン酸塩系、ヒドロキシポリアクリレート、αβ−不飽和ジカルボン酸とオレフィンの共重合体、ポリエチレングリコールモノアルケニルエーテルとマレイン酸系単量体、メタクリル酸単量体から導かれる共重合体、及びスチレン−アクリル酸エステル−マレイン酸系共重合体等のポリカルボン酸が挙げられ、一部架橋反応で高分子化したものや配向ポリマー、高変性ポリマーを含み、これらのうちの一種又は二種以上の使用が可能である。
減水剤の使用量は、セメント100部に対して、固形分換算で0.01〜4部が好ましく、0.05〜2部がより好ましい。0.01部未満では所定の流動性が得難い場合があり、4部を超えると分離や強度遅延を生じる場合がある。
As the water reducing agent, an AE water reducing agent, a high performance water reducing agent, a high performance AE water reducing agent, or the like can be used. Specifically, examples of the AE water reducing agent include a lignin sulfonic acid compound, a modified lignin sulfonic acid compound, a polyol, and an oxycarboxylic acid compound. Examples of the high performance water reducing agent include a formalin condensate of naphthalene sulfonate, Examples include melamine sulfonic acid formalin condensate, and high performance AE water reducing agents include polystyrene sulfonate, hydroxypolyacrylate, αβ-unsaturated dicarboxylic acid and olefin copolymer, polyethylene glycol monoalkenyl ether and maleic. Examples include polycarboxylic acids such as acid monomers, copolymers derived from methacrylic acid monomers, and styrene-acrylic acid ester-maleic acid copolymers, which are partially polymerized by a crosslinking reaction. And oriented polymers, highly modified polymers, one or more of these The above use is possible.
The amount of the water reducing agent used is preferably 0.01 to 4 parts, more preferably 0.05 to 2 parts in terms of solid content, with respect to 100 parts of cement. If it is less than 0.01 part, it may be difficult to obtain a predetermined fluidity. If it exceeds 4 parts, separation or strength delay may occur.
本発明で使用する水の量は、セメント以外の混和材料によって変化するため、一義的には決定することはむずかしいが、通常、セメント100部に対して、20〜70部が好ましく、25〜60部がより好ましい。20部未満では作業性が得られない場合があり、70部を超えると材料分離したり、耐久性が劣る場合がある。 Since the amount of water used in the present invention varies depending on admixtures other than cement, it is difficult to uniquely determine, but usually, 20 to 70 parts are preferable with respect to 100 parts of cement, and 25 to 60 Part is more preferred. If it is less than 20 parts, workability may not be obtained, and if it exceeds 70 parts, material may be separated or durability may be inferior.
セメントなどの投入・混合方法は均一に分散・混合できれば特に限定されるものではない。 There is no particular limitation on the method for charging and mixing cement and the like as long as it can be uniformly dispersed and mixed.
本発明では、セメントなどを投入・混合し、打設し、養生してセメント硬化体を調製する。
混合や、打設条件等は特に限定されるものではない。
In the present invention, cement or the like is charged, mixed, cast, cured, and a hardened cement body is prepared.
Mixing, placing conditions, etc. are not particularly limited.
本発明の膨張材含有のセメントコンクリートからなるセメント硬化体は、JIS A 6202 コンクリート用膨張材付属書2膨張コンクリートの拘束膨張及び収縮試験方法で規定した拘束膨張試験方法によって測定された150×10-6を超える膨張量を有することが好ましい。膨張量が150×10-6未満では充分な乾燥収縮防止効果が得られない場合がある。 Cement cured body made of expanded material containing cement concrete of the invention, JIS A 6202 for concrete expansion material Annex 2 measured by restraining expansion test method prescribed in restraining expansion and shrinkage test method for expanded concrete was 0.99 × 10 - It preferably has an expansion amount exceeding 6 . If the expansion amount is less than 150 × 10 −6 , a sufficient drying shrinkage preventing effect may not be obtained.
本発明では、調製されたセメント硬化体に、合成樹脂水性分散体、水溶性樹脂、膨潤力が20ml/2g以上の高膨潤性粘土鉱物、及び架橋剤を主成分とする養生被覆剤を被覆する。 In the present invention, the hardened cement paste prepared, the synthetic resin aqueous dispersion, a water-soluble resins, nourishing production shall be the main component Rise Junryoku is 20 ml / 2 g or more highly swellable clay mineral, and a crosslinking agent Cover the coating.
本発明で使用する合成樹脂水性分散体とは、一般的には合成樹脂エマルジョンであり、芳香族ビニル単量体、脂肪族共役ジエン系単量体、エチレン系不飽和脂肪酸単量体、及びその他の共重合可能な単量体の内から一種又は二種以上を乳化重合して得られるものである。例えば、スチレンを主体としたスチレン・ブタジエン系ラテックス、スチレン・アクリル系エマルジョンやスチレンと共重合したメチルメタクリレート・ブタジエン系ラテックス、エチレン・アクリルエマルジョンである。合成樹脂エマルジョンには、カルボキシル基またはヒドロキシ基を有するものがより望ましい。
ここで、乳化重合は、重合すべき単量体を混合し、これに乳化剤や重合開始剤等を加え水系で行なう一般的な乳化重合方法である。
膨潤力が20ml/2g以上の高膨潤性粘土鉱物との配合安定性を得るには、アンモニア、アミン類、及びカセイソーダなどの塩基性物質を使用し、pH5以上に調整したものが好ましい。
合成樹脂水性分散体の粒子径は、一般的に100〜300nmであるが、60〜100nm程度の小さい粒子径のものが好ましい。
The synthetic resin aqueous dispersion used in the present invention is generally a synthetic resin emulsion, an aromatic vinyl monomer, an aliphatic conjugated diene monomer, an ethylenically unsaturated fatty acid monomer, and others. The copolymerizable monomer is obtained by emulsion polymerization of one or more of these monomers. For example, styrene / butadiene latex mainly composed of styrene, styrene / acrylic emulsion, methyl methacrylate / butadiene latex copolymerized with styrene, and ethylene / acrylic emulsion. The synthetic resin emulsion is more preferably one having a carboxyl group or a hydroxy group.
Here, the emulsion polymerization is a general emulsion polymerization method in which monomers to be polymerized are mixed, and an emulsifier, a polymerization initiator, and the like are added to the mixture to carry out in an aqueous system.
In order to obtain blending stability with a highly swellable clay mineral having a swelling power of 20 ml / 2 g or more, a basic substance such as ammonia, amines and caustic soda and adjusted to pH 5 or more is preferable.
The particle diameter of the synthetic resin aqueous dispersion is generally 100 to 300 nm, but preferably has a small particle diameter of about 60 to 100 nm.
水溶性樹脂としては、加工澱粉又はその誘導体、セルロース誘導体、ポリビニルアルコール(PVA)などのポリ酢酸ビニルの鹸化物又はその誘導体、スルホン酸基を有する重合体又はその塩、アクリル酸の重合体や共重合体又はこれらの塩、アクリルアミドの重合体や共重合体、ポリエチレングリコール、及びオキサゾリン基含有重合体等が挙げられ、そのうちの一種又は二種以上の使用が可能である。
水溶性樹脂として、純水への溶解度が常温で1%以上であるものであれば良く、樹脂単位重量当たりの水素結合性基又はイオン性基が10〜60%であることが好ましい。
また、平均分子量は2,000〜1,000,000が好ましい。
水溶性樹脂の使用量は、合成樹脂水性分散体の固形分100部に対して、固形分換算で0.05〜200部が好ましい。0.05部未満では防湿性が低下する場合があり、200部を超えると防湿性が著しく低下する場合がある。
Examples of water-soluble resins include modified starch or derivatives thereof, cellulose derivatives, saponified products of polyvinyl acetate such as polyvinyl alcohol (PVA) or derivatives thereof, polymers having sulfonic acid groups or salts thereof, polymers of acrylic acid, and copolymers. Examples include polymers or salts thereof, acrylamide polymers and copolymers, polyethylene glycol, and oxazoline group-containing polymers, and one or more of them can be used.
Any water-soluble resin may be used as long as it has a solubility in pure water of 1% or more at room temperature, and the hydrogen bonding group or ionic group per unit weight of the resin is preferably 10 to 60%.
The average molecular weight is preferably 2,000 to 1,000,000.
The amount of the water-soluble resin used is preferably 0.05 to 200 parts in terms of solid content with respect to 100 parts of solid content of the synthetic resin aqueous dispersion. If it is less than 0.05 part, the moisture resistance may be reduced, and if it exceeds 200 parts, the moisture resistance may be significantly reduced.
膨潤力が20ml/2g以上の高膨潤性粘土鉱物(以下、単に高膨潤性粘土鉱物という)の鉱物としては、スクメタイト属に属する層状ケイ酸塩鉱物が挙げられる。例えば、モンモリロナイト、バイデライト、ノントロナイト、サポナイト、マイカ、及びベントナイトなどである。これらは天然品、合成品、及び加工処理品のいずれであっても使用可能である。
そのうち、本発明では、日本ベントナイト工業会、標準試験方法 JBAS-104-77に準じた方法での膨潤力が20ml/2g以上の粘土鉱物を使用する。特に、日本ベントナイト工業会、標準試験方法 JBAS-104-77に準じた方法での膨潤力が20ml/2g以上の合成マイカや、膨潤力が20ml/2g以上のベントナイトが好ましい。
また、イオン交換当量が100g当たり、10ミリ当量以上のものが好ましく、60〜200ミリ当量以上のものがより好ましい。
さらに、そのアスペクト比が50〜5,000のものが好ましい。アスペクト比とは、電顕写真により求めた層状に分散した粘土鉱物の長さ/厚みの比である。
高膨潤性粘土鉱物の使用量は、合成樹脂水性分散体の固形分100部に対して、固形分に対して、1〜50部が好ましい。1部未満では防湿性が低下しブロッキングが生じやすくなる場合があり、50部を超えると防湿性被覆剤の膜の変形能力が低下する場合がある。
Examples of minerals of highly swellable clay minerals (hereinafter simply referred to as “highly swellable clay minerals”) having a swelling power of 20 ml / 2 g or more include layered silicate minerals belonging to the scumite genus. For example, montmorillonite, beidellite, nontronite, saponite, mica and bentonite. Any of natural products, synthetic products, and processed products can be used.
Among them, in the present invention, a clay mineral having a swelling power of 20 ml / 2 g or more by a method according to the Japan Bentonite Industry Association, standard test method JBAS-104-77 is used. In particular, synthetic mica having a swelling power of 20 ml / 2 g or more according to a method in accordance with Japan Bentonite Industry Association, standard test method JBAS-104-77, or bentonite having a swelling power of 20 ml / 2 g or more is preferred.
Further, per 100g ion exchange equivalent, preferably not less than 10 milliequivalents, more preferably not less than 60 to 200 milliequivalents.
Furthermore, those having an aspect ratio of 50 to 5,000 are preferred. The aspect ratio is the length / thickness ratio of the clay mineral dispersed in layers obtained by electron micrograph.
The amount of the highly swellable clay mineral used is preferably 1 to 50 parts with respect to the solid content with respect to 100 parts of the solid content of the synthetic resin aqueous dispersion. If it is less than 1 part, the moisture resistance may be reduced and blocking may occur easily. If it exceeds 50 parts, the deformability of the film of the moisture-proof coating may be reduced.
架橋剤とは、水溶性樹脂や合成樹脂水性分散体が有するカルボキシル基、アミド基、及び水酸基等の親水性官能基と反応して、架橋、高分子化(三次元網目構造)、又は疎水化するものであり、カルボキシル基と付加反応を起こすオキサゾリン基を有するものが水溶性樹脂をも兼ねるので好ましい。
架橋剤の使用量は、合成樹脂水性分散体と水溶性樹脂の合計の固形分100部に対して、固形分換算で0.01〜30部が好ましい。0.01部未満では防湿性が低下する場合があり、30部を超えると防湿性やブロッキング防止性が頭打ちになる。
A cross-linking agent reacts with a hydrophilic functional group such as a carboxyl group, an amide group, and a hydroxyl group contained in an aqueous dispersion of a water-soluble resin or synthetic resin to crosslink, polymerize (three-dimensional network structure), or hydrophobize. Those having an oxazoline group that undergoes an addition reaction with a carboxyl group also serve as a water-soluble resin, and are preferable.
The amount of the crosslinking agent used is preferably 0.01 to 30 parts in terms of solid content with respect to 100 parts of the total solid content of the synthetic resin aqueous dispersion and the water-soluble resin. If it is less than 0.01 part, the moisture resistance may be lowered, and if it exceeds 30 parts, the moisture resistance and the blocking resistance reach a peak.
本発明では、合成樹脂水性分散体、水溶性樹脂、高膨潤性粘土鉱物、及び架橋剤を混合して、養生被覆剤を調製する。 In the present invention, the synthetic resin aqueous dispersion, by mixing with a water-soluble resins, highly swellable clay mineral, and a crosslinking agent, to prepare a curing coatings.
養生被覆剤の合成方法は、水溶性樹脂と高膨潤性粘土鉱物をあらかじめ水中で混合した後に、合成樹脂水性分散体と架橋剤を混合する方法が好ましい。 Synthesis method of curing the coating agent, after the water-soluble resin and highly swellable clay mineral were premixed in water, a method of mixing the synthetic resin aqueous dispersion crosslinking agent is preferred.
養生被覆剤の被覆方法は、均一に養生被覆膜が形成できる方法であれば特に限定されるものではなく、撒布したり、塗布したり、吹付けたりすることが可能である。
養生被覆剤は、水平のセメントコンクリート部材であれば、ブリーデング終了後に撒布や被覆することが可能である。
また、撒水等の水に関する養生が終了後、できるだけ早い時期に被覆することが膨張材や乾燥収縮低減剤の効果を得るために望ましい。
養生被覆剤の被覆量は固形分換算で4〜160g/m2が好ましい。4g/m2未満では養生効果が認められず、160g/m2を超えると、コストや労力のわりに養生効果が頭打ちになる。
The coating method of the curing coating agent is not particularly limited as long as the curing coating film can be uniformly formed, and can be distributed, applied, or sprayed.
If the curing coating is a horizontal cement-concrete member, it can be spread or coated after the bleeding.
In addition, it is desirable to coat as soon as possible after completion of water curing such as flooding in order to obtain the effects of the expansion material and the drying shrinkage reducing agent .
The coating amount of the curing coating agent is preferably 4 to 160 g / m 2 in terms of solid content . If it is less than 4 g / m 2 , the curing effect is not recognized, and if it exceeds 160 g / m 2 , the curing effect reaches its peak for cost and labor.
以下、本発明を実施例に基づいて説明する。 Hereinafter, the present invention will be described based on examples.
実験例1
セメントと膨張材の合計100部に対して、水40部と減水剤0.5部に、セメント100部に対して、表1に示す膨張材を、さらに、細骨材100部をミキサに投入し、高速の合計時間90秒練り混ぜを行い、モルタルを調製した。モルタルのフローは260±10mm、空気量は2.0±0.5%、温度は20℃であった。
一方、合成マイカをイオン交換水に固形分4%となるように分散させ、さらに、80℃加温後、ホモジナイザーで攪拌し、膨潤性粘土の分散液得た。
これにPVA水溶液を混合した後、エチレンアクリルエマルジョンを合成樹脂水性分散体/高膨潤性粘土鉱物/水溶性樹脂/架橋剤の固形分比率を100/10/5/10になるように調整し、濃度40%の養生被覆剤αを作製した。
同様に、合成樹脂水性分散体/高膨潤性粘土鉱物/水溶性樹脂/架橋剤の固形分比率を100/10/5/0になるように調整し、濃度40%の養生被覆剤βを作製した。
比較例のため、市販のSBRラテックスのエマルジョンを養生被覆剤γとして、同様に行った。
調製したモルタルを成形し、材齢1日後に脱型し、養生被覆剤を刷毛で被覆し、硬化体の長さ変化量を測定し、長さ変化測定供試体を用いて曲げひび割れ強度と圧縮強度を測定した。被覆量、測定結果を表1に併記する。
Experimental example 1
For a total of 100 parts of cement and expansion material, 40 parts of water and 0.5 parts of water reducing agent, 100 parts of cement, the expansion material shown in Table 1 and 100 parts of fine aggregate are put into a mixer. The mortar was prepared by mixing at high speed for 90 seconds. The mortar flow was 260 ± 10 mm, the air volume was 2.0 ± 0.5%, and the temperature was 20 ° C.
On the other hand, synthetic mica was dispersed in ion-exchanged water so as to have a solid content of 4%, and further heated at 80 ° C. and stirred with a homogenizer to obtain a dispersion of swellable clay.
After mixing the PVA aqueous solution, the ethylene acrylic emulsion was adjusted so that the solid content ratio of synthetic resin aqueous dispersion / highly swellable clay mineral / water-soluble resin / crosslinking agent was 100/10/5/10, A curing coating α having a concentration of 40% was prepared.
Similarly, the solid content ratio of the synthetic resin aqueous dispersion / highly swellable clay mineral / water-soluble resin / crosslinking agent is adjusted to 100/10/5/0 to produce a curing coating β having a concentration of 40%. did.
For comparison, a commercially available SBR latex emulsion was used in the same manner as the curing coating γ.
Molding the prepared mortar, demolding after 1 day of age, covering the curing coating with a brush, measuring the length change of the cured body, bending crack strength and compression using the length change measurement specimen The strength was measured. Table 1 shows the coating amount and the measurement results.
<使用材料>
セメント :普通ポルトランドセメント、市販品
膨張材A :カルシウムサルフォアルミネート系膨張材、市販品、ブレーン値3,500cm2/g
膨張材B :カルシウムアルミノフェライト系膨張材、市販品、ブレーン値3,500cm2/g
減水剤 :高性能AE減水剤、ポリカル系、市販品
細骨材 :川砂、5mm下、密度2.60g/cm3
合成樹脂水性分散体:エチレンアクリル酸共重合エマルジョン、市販品、分子量27,500、アクリル酸/エチレン共重合比15/85
合成マイカ:市販品、膨潤度30ml/2g、カチオン交換能54meq/100g
PVA水溶液:ポリビニルアルコール、鹸化度98%以上、重合度500、10%水溶液
架橋剤 :ポリオキサゾリン、市販品
SBRラテックス:市販品、固形分50%
<Materials used>
Cement: Ordinary Portland cement, commercially available expanded material A: Calcium sulfoaluminate-based expanded material, commercially available, Blaine value 3,500 cm 2 / g
Expansion material B: Calcium aluminoferrite-based expansion material, commercially available, brain value 3,500 cm 2 / g
Water-reducing agent: High-performance AE water-reducing agent, polycal, commercially available fine aggregate: river sand, 5mm below, density 2.60g / cm 3
Synthetic resin aqueous dispersion: ethylene acrylic acid copolymer emulsion, commercial product, molecular weight 27,500, acrylic acid / ethylene copolymer ratio 15/85
Synthetic mica: Commercial product, swelling degree 30ml / 2g, cation exchange capacity 54meq / 100g
PVA aqueous solution: polyvinyl alcohol, saponification degree 98% or more, polymerization degree 500, 10% aqueous solution cross-linking agent: polyoxazoline, commercial product SBR latex: commercial product, solid content 50%
<測定方法>
長さ変化量:JIS A 6202 モルタル法に準じ測定
曲げひび割れ強度:JIS R 5201 に準じ測定
圧縮強度 :JIS R 5201 に準じ測定
<Measurement method>
Length change: Measured according to JIS A 6202 mortar method Bending crack strength: Measured according to JIS R 5201 Compressive strength: Measured according to JIS R 5201
表1より、本発明の方法を用いると、材齢初期で安定した膨張量と乾燥収縮が少なくひび割れ抵抗性が高い硬化体が得られることが判る。 From Table 1, it can be seen that when the method of the present invention is used, a cured product having a small amount of expansion and drying shrinkage that is stable at the early stage of age and high crack resistance can be obtained.
実験例2
セメント292kgと膨張材20kgの合計単位量を312kg/m3とし、さらに、細骨材727kg/m3と粗骨材1,134kg/m3とをミキサに投入し、10秒間空練りし、その後、減水剤とAE助剤を含む水142kg/m3を投入し、90秒間2軸ミキサを使用し練り混ぜ、コンクリートを調製した。コンクリートのフレシュ性状である、スランプの測定値は18±0.5cm、空気量は4.5±0.5%、温度は20±2℃の範囲内であった。
フレシュコンクリートの硬化まで乾燥しないようにシートで覆い、20℃の室内で材齢1日まで養生し、脱型後材齢7日まで水中養生を行った。
その後、養生被覆剤を刷毛を用い被覆し、硬化体の長さ変化量を測定し、長さ変化測定供試体を用いて曲げひび割れ強度と圧縮強度を測定した。被覆量と測定結果を表2に併記する。
Experimental example 2
The total unit amount of cement 292kg expansion material 20kg and 312kg / m 3, further charged with a fine aggregate 727kg / m 3 and coarse aggregate 1,134kg / m 3 to the mixer, air-kneaded for 10 seconds, then, 142 kg / m 3 of water containing a water reducing agent and an AE auxiliary agent was added, and the mixture was mixed for 90 seconds using a biaxial mixer to prepare concrete. The measured value of slump, which is the fresh property of concrete, was 18 ± 0.5 cm, the amount of air was 4.5 ± 0.5%, and the temperature was in the range of 20 ± 2 ° C.
The sheet was covered with a sheet so as not to be dried until the fresh concrete was cured, and was cured in a room at 20 ° C. until the age of 1 day, and was cured under water until the age of 7 days after demolding.
Thereafter, the curing coating agent was coated with a brush, the amount of change in the length of the cured body was measured, and the bending crack strength and the compressive strength were measured using the length change measurement specimen. Table 2 shows the coating amount and the measurement result.
<使用材料>
粗骨材 :砕石、Gmax20mm、密度2.65g/cm3
AE助剤 :アルキルアリルスルホン酸化合物、市販品
<Materials used>
Coarse aggregate: Crushed stone, Gmax 20 mm, density 2.65 g / cm 3
AE auxiliary agent: Alkyl allyl sulfonic acid compound, commercial product
<測定方法>
長さ変化量:JIS A 6202 コンクリート法に準じて測定
曲げひび割れ強度:JIS A 1106 に準じ測定
圧縮強度 :JIS A 6202 コンクリートの圧縮強度試験方法に準じて測定
<Measurement method>
Length variation: JIS A measuring flexural crack strength according to 6202 concrete method: measuring the compressive strength according to JIS A 1106: Measured in accordance with Test Method of Compressive Strength for JIS A 6202 Concrete
表2より、本発明の方法は、コンクリートにおいても、高いひび割れ抵抗性を有することが判る。 From Table 2, it can be seen that the method of the present invention has high crack resistance even in concrete.
実験例3
セメント100部に対して、表3に示す乾燥収縮低減剤、水40部、及び減水剤0.5部をミキサに投入し、セメント100部と細骨材100部を混合し、高速の合計時間90秒練り混ぜを行い、モルタルを調製したこと以外は実験例1と同様に行った。結果を表3に併記する。
調製したモルタルを成形し、材齢1日後に脱型し、養生被覆剤を刷毛で被覆し、硬化体の長さ変化量を測定し、長さ変化測定供試体を用いて曲げひび割れ強度と圧縮強度を測定した。被覆量、測定結果を表3に併記する。
Experimental example 3
Per 100 parts of cement, drying shrinkage-reducing agent shown in Table 3, 40 parts of water, 0.5 parts of beauty down liquid medication及were charged into a mixer, by mixing 100 parts of cement and fine aggregate 100 parts, fast total time perform kneading 90 seconds, except that to prepare a mortar was conducted in the same manner as in experimental example 1. The results are also shown in Table 3.
Molding the prepared mortar, demolding after 1 day of age, covering the curing coating with a brush, measuring the length change of the cured body, bending crack strength and compression using the length change measurement specimen The strength was measured. Table 3 shows the coating amount and the measurement results.
<使用材料>
乾燥収縮低減剤イ:低分子量エチレンオキサイドとプロピレンオキサイドの共重合物を成分とする市販品
乾燥収縮低減剤ロ:低級アルコールのアルキレン付加物を成分とする市販品
<Materials used>
Drying shrinkage reducing agent a: Commercial product comprising a copolymer of low molecular weight ethylene oxide and propylene oxide as a component Dry shrinkage reducing agent b: Commercial product comprising an alkylene adduct of a lower alcohol as a component
表3より、本発明の方法を用いると、材齢初期で安定した膨張量と乾燥収縮が少なくひび割れ抵抗性が高い硬化体が得られることが判る。 From Table 3, it can be seen that when the method of the present invention is used, a cured product having a small amount of expansion and drying shrinkage that is stable at the early stage of age and high crack resistance can be obtained.
実験例4
セメント単位量を312kg/m3とし、さらに、細骨材727kg/m3と粗骨材1,134kg/m3とをミキサに投入し、10秒間空練りし、その後、乾燥収縮低減剤イ12kg/m3、減水剤とAE助剤を含む水142kg/m3を投入し、90秒間2軸ミキサを使用し練り混ぜ、コンクリートを調製したこと以外は実験例2と同様に行った。結果を表4に併記する。
Experimental Example 4
Cement unit amount and 312kg / m 3, further charged with a fine aggregate 727kg / m 3 and coarse aggregate 1,134kg / m 3 to the mixer, air-kneaded for 10 seconds, then Drying shrinkage reducing agent Lee 12kg / m 3, charged with water 142 kg / m 3 comprising water reducing agent and AE aid kneaded using 90 seconds biaxial mixer, except that the prepared concrete was conducted in the same manner as in experiment example 2. The results are also shown in Table 4.
表4より、本発明の方法は、コンクリートにおいても、高いひび割れ抵抗性を有することが判る。 From Table 4, it can be seen that the method of the present invention has high crack resistance even in concrete.
実験例5
グラウト材に、メーカー指定標準水量とハンドミキサーを使用して練り上げたモルタルを、100×100cmの目荒らしされた各コンクリート平板上に、厚さが1cmになるように施工を行った。モルタル硬化まで屋内でシートで覆い、翌日に、養生被覆剤を150g/m2 (固形分換算で60g/m 2 )を塗布し、モルタルのひび割れの発生比較試験を屋内にて行った。目視で判断できる0.04mm以上のひび割れ発生材齢日とした。結果を表5に併記する。
比較のため、塗布しない場合も同様に行った。
Experimental Example 5
The mortar kneaded with grout material using the standard water amount specified by the manufacturer and a hand mixer was applied to each of the concrete plates flattened by 100 x 100 cm so that the thickness would be 1 cm. The sheet was covered indoors until the mortar was cured, and the curing coating was applied 150 g / m 2 (60 g / m 2 in terms of solid content ) on the next day, and a mortar cracking comparison test was conducted indoors. The cracking material age was 0.04 mm or more, which can be judged visually. The results are also shown in Table 5.
For comparison, the same procedure was performed when no coating was applied.
<使用材料>
グラウト材:市販品、カルシウムサルフォアルミネート系膨張材、セメント、及び骨材の混合物
<Materials used>
Grout: A mixture of commercial products, calcium sulfoaluminate-based expansion material, cement, and aggregate
表5より、本発明の方法は、コンクリートにおいても、高いひび割れ抵抗性を有することが明らかである。 From Table 5, it is clear that the method of the present invention has high crack resistance even in concrete.
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